Stereoselective synthesis of a C-glycosylic compound (a “methyl C-glycoside”) through a regioselective free-radical ring-opening reaction. A single-crystal X-ray structure determination

Readily available 3,4,6-tri-O-acetyl-d-glucal was converted to 2,6-anhydro-5,7-O-benzylidene-1,3,4-trideoxy-d-arabino-hept-3-enitol, a methyl C-glycosylic compound. Cyclopropanation of 4,6-O-benzylidene-d-glucal, followed by tributylstannyl radical-mediated regioselective ring opening of the 1,2-cyclopropano sugar led to a 2,6-anhydro-1-deoxyheptose, (a “methyl C-β-d-glycoside”). The stereochemistry of the 1,2-cyclopropano sugar and the “methyl C-glycoside” were confirmed by single-crystal X-ray diffraction studies.